Petroleum sulphonyl chlorides



Patented Jan. 3, 1939 I UNITED STATES OFFlCE delphia, Pa., assignors to Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application October 30, 1937, Serial N- 171,908

8 Claims. (01. 260 -543) This invention relates to mixed sulphonylchlotained by treating kerosene, naphtha, paraflln rides of petroleum hydrocarbons which contain oil, petrolatum, paraflln wax, and lubricating oils not less than twelve carbon atoms in the moleof an essentially parafllnic or naphthenic charcule. These sulphonyl chlorides possess the genacter with chlorine. These chlorinate materials eral properties of being water-insoluble, heavy, are usually obtained by heating the oils or waxes 5 viscous oils or waxy solids which readily are to about 100 C. and passing in dry chlorine, convertible to the corresponding sulphonates, sulpreferably in the presence of catalysts such as phonic acids, sulphonamides or sulphonic acid iodine, until the desired degree of chlorination esters by treatment respectively with hydroxides is reached. v

10 or carbonates of metals, water, ammonia or pri- From these materials, mixed sulphonyl cblol0 mary or secondary amines, and alcohols. They rides are obtained containing from 12 to upwards are useful intermediates for preparing capillaryof 80 carbon atoms in the molecule, depending active compounds, as their water-soluble derivaupon the fractions of the petroleum used. The tives possess foaming, wetting, emulsifying, and chlorinated kerosenes will yield mixed sulphonyl l5 cleansing properties. chlorides having from about 12 to 30 carbon 15 These aliphatically-bound mixed sulphonyl atoms, while the higher boiling paraflin waxes chlorides of higher petroleum hydrocarbons are and lubricating oils and petrolatum will yield readily obtained in good yields by a modificasulphonyl chlorides of from about to 80 cartion of the process developed by Treat B. Johnbon atoms or thereabouts. The chlorinated pe- 20 son and described in his application Serial No. troieum fractions used may be saturated or un- 20 72,983, filed April 6, 1936. saturated in character.

According to the present invention a petroleum In order to more fully describethis inventio hydrocarbon mixture containing not less than the following examples are given:

twelve carbon atoms is chlorinated until at least p mixture of -5 of 6 01 101!!!- one atomic weight of chlorine is introduced for d p ff n w x c ntaining 14.5% chlorine), 5 each mol. of hydrocarbon. Two or more chlorine 6 gthiourea and 2 0 cc- Of butanol was boiled atoms may be introduced if desired. This chlounder reflux for 21 hours, after which thebutanol rinated petroleum mixture is then heated with was removed by vacuum distillation. The parthiourea preferably in a high boiling organic affin pseudo-thiourea hydrochloride was dissolvent, such as butanol, until a sample of the solved in 1500 cc. of water and stirred rapidly 3 product is completely soluble in water. This while dry chlorine was passed into the solution usually requires from 8 to 22 hours boiling. The until no more chlorine was absorbed. The disolvent is then distilled off, leaving behind a sulphonyl chloride separated a white W viscous, resinous mass of the pseudo-thiourea hywhich was washed and drieddrochlorides of the petroleum hydrocarbon mix- Upon boiling t s al w th 5% caustic 5 t ed, Thi at l i dissolved or soda solution, the corresponding sodium sulphonpended in water and the solution is chlorinated ate 0f the m wax was Obtained- It ca b at ab ut 10-20 0,, whi h causes th mixed 1- salted out from its diluted aqueous solution by phonyl chloride of the petroleum oil to sepameans of sodium chloride. When dried, it forms rate from the water in the form of a pale yela brownish powderable solid containing aproxi- 40 low or white heavy oil or wax. It may be washed two sulphonic a d roups per avera t l water and can be stored for a mol. of paraffin wax. It is easily soluble in water siderable period of time without change. Or it to give a py 5011mm!- can be dissolved in an inert organic solvent such Example mixture conslsting 01 238 8- as ether, and the water therein separated memono'chlorinatedparaffinwax (ntam1ng7-97% 46 chanically or by anhydrous sodium sulphat or C1), 39 g. thiourea and 250 cc. of butanol, was other suitable dehydrating agent. The product boiled under reflux for 21 hours and Worked up necessarily contains the aliphatically-bound sulas above- The paraffin -s p o yl ch 0- phonyl chlorides of all of the hydrocarbon comride sep ed as a Whi e Wa The mono-sodi- 50 ponents of the oil used, and is, of course, a comum sulp onate 0f Darafiln wax which is obtained 50 plex mixture of sulphonyl chlorides. by boiling this sulphonyl chloride with caustic For the purpose of this invention, we use asv soda forms a white, viscous paste having a. fatty raw materials the mono-chlorinated or polyfeel. It is soluble in hot water and G ls O 6 0 chlorinated petroleum oils and waxes containing ing. It is useful as an emulsifying agent and not less than 12 carbon atoms, such as are ob- I for softening cotton or rayon.

The paramn sulphonamide obtained from the above sulphonyl chloride by treatment with ammonia formed a thick oil.

By heating the parafiln sulphonyl chloride with triethanolamine, the corresponding paraflin sulphonic acid ester of triethanolamine was obtained. It formed a water-soluble oil having soap-like properties.

By using 140 g. of chlorinated paraflln wax (containing 25.5% C1) and 76 g. thiourea as above, there was obtained paraflintrisulphonyl chloride as a pale yellow, heavy oil.

The tetra sulphonyl chloride can be obtained as a pale yellow, heavy oil by using 85 g. chlorinated paraihn wax (containing 42.2% C1) and 76 g. thiourea.

Example 3.Commercial tri-isobutylene obtainable by the polymerization of isobutylene and containing a number of isomers having the composition C12H24 was chlorinated at 50 C. until an amount of chlorine was absorbed equal to one atomic equivalent.

200 g. of this chlorinated material was heated with 75 g. thlourea and 200 cc. butanol for 18 hours, under reflux. The butanol was removed by distillation under reduced pressure. The residue was dissolved in 1000 cc. of water and'the solution. was saturated with chlorine at 10-20 C. while stirring rapidly. The sulphonyl chloride separated as a yellowish heavy oil.

When boiled with water, it gave a solution of the corresponding sulphonic acid useful as a capillary-active compound. In a similar manner, chlorinated tetra isobutylene yields the mixed sulphonyl chlorides of a C16 mixture of oleflnes. I

Example 4.A mixture consisting of 250 g. of chlorinated petrolatum (containing 15% chicrine) 80 g. thiourea and 250 cc. of butanol was boiled under reflux for 20 hours. The. product was worked up as in Example 1 to yielda petrolatum sulphonyl chloride, as a yellowish thick oil.

Example 5.-A mixture consisting of 250 g. of chlorinated kerosene containing 15% of chlorine, was heated with 80 g. of thiourea and 250 cc. of butanol under reflux for 20 hours. The product was worked up as set forth in Example 1. The kerosene sulphonyl chloride was obtained as a pale yellow, thick oil.

Lubricating oils or-petroleum naphtha may likewise be treated to yield mixed aliphatic or hydroaromatic sulphonyl chlorides of high carbon content. Any petroleum fraction composed primarily of molecules having not less than 12 carbon atoms which is capable of chlorination is suitable for the purpose of this invention. The

petroleums used may be crude or refined and may contain aromatics as impurities. Any nuclear chlorinated aromatics formed do not undergo the condensation with thiourea and are easily separated from the water-soluble pseudo-thioureas of the chlorinated aliphatic and hydroaromatic bodies. However, if alkylated or cyclo-alkylated aromatic hydrocarbons are present in the petroleum used, any aliphaticallybound chlorine in these compounds will readily form pseudo-thioureas and consequently be converted to sulphonyl chlorides.

We claim:

1. A mixture of the sulphonyl chlorides of the aliphatic and cycloaliphatic hydrocarbons con tained in a petroleum fraction composed primarily of molecules havingnotless than twelve carbon atoms.

2. A mixture of the sulphonyl chlorides of the aliphatic and cycloaliphatic hydrocarbons contained in paraffin wax.

3. A mixture of the sulphonyl chlorides of the aliphatic and cycloaliphatic hydrocarbons contained in kerosene.

4. A mixture of the sulphonyl chlorides of the aliphatic and cycloaliphatic hydrocarbons contained in a petroleum oil composed primarily of molecules having not less than twelve carbon atoms.

5. A mixture of aliphatic and cycloaliphatic sulphonyl chlorides having not less than twelve carbon atoms resulting from the chlorination in an aqueous solvent of the mixed pseudothiourea hydrohalides derived from the reaction of thiourea with the corresponding chlorinated petroleum hydrocarbons containing not less than twelve carbon atoms.

6. The process which comprises reacting a chlorinated petroleum fraction composed primarily of aliphatic and cycloaliphatic molecules having not less than twelve carbon atoms with thiourea, dissolving the resulting pseudothiourea hydrochloride in water and passing the chlorine through the solution.

'7. The process which comprises reacting a chlorinated paraffin wax with thiourea, dissolving the resulting pseudothiourea hydrochloride in Water and passing the chlorine through the solution.

8. The process which comprises reacting a chlorinated kerosene with thiourea, dissolving the resulting pseudothiourea hydrochloride in water and passing the chlorine through the solution.

HERMAN A. BRUSON. JOHN W. EASTES. 

